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Thermal Conductivity of Silicone Rubber Filled With ZnO

Qiuhong Mu, Shengyu Feng, Guangzhao Diao

Department of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People’s Republic
of China

Thermal conductivities of silicone rubber filled with ZnO rubber with good thermal conductivities [11, 13–18]. The
in a wide volume range were measured in order to study advantages of conductive rubber, when compared with metals
the effect of formed conductive particle chains on ther-
mal conductivities. With the increasing of content of ZnO
(typically used) include improved corrosion resistance, lighter
particles in silicone rubber, the amount of formed con- weight, and the ability to adapt the conductivity properties to
ductive chains increases and the conductive chains tend suit the application needs. Such thermally conductive silicone
linearly to increase the thermal conductivity of the com- rubbers are widely used in aviation, electronic devices, and so
posite. The experimental results obtained were also an- on.
alyzed using the Nielsen and Agari models to explain the
effect of ZnO filler on the formation of thermal conduc- In previous studies, published data on the thermal con-
tive networks. Thermal conductivities of a polymer filled ductivity of filled silicone rubber are limited and concerned
with high volume content of particles evidently in- mainly with the behavior between thermal conductivities of
creased with the adding of small size fillers. The scan- composites and volume contents of thermally conductive
ning electron microscopy (SEM) showed that percola- fillers [19 –22]. Although a large quantity of filler can be
tion threshold has been reached at 31.4 vol% ZnO filler
loading, and the hybrid fillers are more densely packed added to improve the thermal conductivity of silicone rub-
than single fillers in the silicone rubber matrix. There ber, too much filler often decreases some other properties,
occurs a positive temperature coefficient (PTC) phe- such as strength and elasticity, and makes processing and
nomenon in thermal resistance in composites of silicone application more difficult. It is very clear that there is a
rubber filled with ZnO. POLYM. COMPOS., 28:125–130, 2007.
© 2007 Society of Plastics Engineers
contradiction between high thermal conductivity and good
processing behavior, which should be solved.
It has been reported that the thermal conductivity of
INTRODUCTION polymers was improved by filling with various types of
Thermal conductive elastomers usually employ vulcanized particles and many thermal conductive models have been
rubber as a matrix for dispersion of thermally conductive fillers proposed for two-phase system [23–31]. In general, thermal
including metal powders, such as Al, Ag, and Cu [1–5]. Stain- conduction systems in polymers filled with high conductive
less steel, carbon, graphite powders, and inorganic particles are particles vary with the volume content of particles and can
also frequently employed as thermally conductive fillers be classified into two systems. One is a system with low
[6 –10]. The fillers improve not only the thermal conductivity content of particles, in which dispersed particles hardly
of elastomers but also their mechanical properties and thermal touch each other (dispersed system). The Maxwell-Eucken,
stabilities [11]. Silicone elastomers are often used as a polymer Bruggeman, and Cheng-Vochan models [30] can be applied
matrix for preparation of thermally conductive composites, to the thermal conductivity of a composite in this system.
because they are stable in a wide range of temperatures and The other is a system with higher content, in which con-
have excellent weather and chemical resistance properties [11, ductive chains are exponentially formed by particles and
12]. Typical pure silicone rubber usually has poor thermal contribute to a large increase in thermal conductivity of a
conductivities (0.165 W/m 䡠 K). However, when filled with composite (attached system). The Agari [28] and Nielsen
thermally conductive fillers, such as metal powders, graphite, [26] models can be used in this system.
Al2O3, SiC, BN, and ZnO, they can be made into silicone In this study, silicone rubber filled with highly thermal
conductive but electrical insulating filler zinc oxide (ZnO)
fillers at various loadings up to 35 vol% were prepared. The
Correspondence to: Shengyu Feng; e-mail: fsy@sdu.edu.cn effects of ZnO fillers at various filler loadings on the ther-
Contract grant sponsors: Foundation for University Key Teacher, Ministry mal conductivities of the silicone rubber were studied. Ex-
of Education; Reward Funds for the Outstanding Young, Shandong Uni- perimental data obtained was fitted into the model equa-
versity, Ministry of Education.
DOI 10.1002/pc.20276
tions, namely Nielsen and Agari for thermal conductivity.
Published online in Wiley InterScience (www.interscience.wiley.com). To obtain maximum thermal conductivities of composites
© 2007 Society of Plastics Engineers with limited filler content, we make different particle sizes

POLYMER COMPOSITES—2007
TABLE 1. Properties of ZnO fillers. TABLE 2. Physical properties of thermally conductive silicone rubber.

Average particle Density Thermal conductivity Assay ZnO Tensile Elongation


Fillers size (␮m) (g/cm3) (W/m K) (% ZnO) loading strength at break Hardness
Sample (vol%) (MPa) (%) (shore A)
1# 76–78 5.60 60 ⬎99
2# 37–39 5.61 60 ⬎99.7 1 0 5.57 378.4 46
3# 0.15 5.61 60 ⬎99.9 2 4.3 5.81 289.1 42
3 8.3 6.58 288.4 46
4 12.0 6.24 301.2 50
5 18.5 5.61 277.6 54
of ZnO closely packed in the silicone rubber, and we got 6 24.1 4.30 156.8 62
7 26.6 4.81 154 64
silicone rubber that has higher thermal conductivity with
8 31.2 4.32 133.6 70
lower volume content. Finally, the variations of thermal 9 34.6 4.15 97.2 76
conductivities of silicone rubber with a rise in temperature
were also determined.

where K is the thermal conductivity of thermal pads (W


EXPERIMENTAL PROCEDURES m⫺1 K⫺1), Q the heat flux generated by the specimen (W),
Thot_int the interface temperature of the heating calorimeter
(K), Tcold_int the interface temperature of the cooling calo-
Materials
rimeter (K), A the surface area of tested thermal pads (m2),
Methylvinylsilicone gum (Mn 5.8 ⫻ 105; mole content of and h the thickness of thermal pads (m). The average heat
vinyl group, 0.15%), silica, ZnO, and 2,5-bis(tert-butyl per- flux (Q) is the amount of heat generated by two cartridge
oxy)-2,5-dimethyl hexane(DBPMH) were supplied by heaters. When equilibrium is achieved, the heat flux of
Chenguang Institute of Chemical Industry (Chengdu, specimen is that of the cold block. If we measure the heat
China), Cabot China (Shanghai, China), Zhongxin Chemi- flux of the cold block at this time, Q can be obtained. The
cal Industry (Zibo, China), and Tianjin Akzo Nobel Perox- measurements were mainly performed at 75°C, and at var-
ides (Tianjin, China), respectively. The properties of ZnO ious temperatures between 75 and 135°C to determine the
are listed in Table 1. variation of conductivity with temperature.
Morphological observations on the thermal conductive
silicone rubber were done using the scanning electron mi-
Preparation of Conductive Silicone Rubber croscope (SEM), JEOL JSM-7600F. To study the filler
According to the literature [32, 33], materials were com- distribution and morphology, observations were carried out
pounded and then vulcanized at 170°C for 20 min under a on the tensile broken surface of ZnO filled thermal conduc-
pressure of 9.8 MPa. The vulcanized samples were post- tive silicone rubber.
cured at 190°C for 3 h. The samples were left standing
before testing (24 h maturation at room temperature).
RESULTS AND DISCUSSION
Testing
Thermal conductivities of silicone rubber were tested Thermal Conductivity of Silicone Rubber Filled With
with a thermally conductive probe instrument RTC-C (Ron- Various Volume Content of ZnO
ghua Electronic Instrument Manufacture, Jiangsu, China)
by the stable state method. The size of the specimen is 13.0 Table 2 summarizes some of the physical properties of
cm in diameter and 0.20 cm in thickness. Measurements the thermal conductive silicone rubber (filled with 1#ZnO).
were carried out with the thermal pads clamped between the The tensile strength and elongation at break of silicone
two calorimeters. Then, two thermocouples were used to rubber increased initially with increasing volume content of
determine the respective temperature of the two blocks. ZnO in the range of 0 –12 vol% and then decreased. The
When thermal equilibrium is achieved between the blocks reason is that the thermal conductive filler ZnO is also a
and the specimen, the thermal conductivity of the specimen kind of half reinforcing filler, which can improve the me-
was calculated from the Fourier’s law, as is shown in Eq. 1, chanical strength with low volume content. But when ZnO
based on the assumption that the heat flow is one-dimen- particles were added with large volume content, the tensile
sional in the perpendicular direction, and no heat loss occurs strength and elongation at break decreased for the poor
in the lateral direction: interfacial interaction between ZnO and silicone rubber
matrix. Especially, when the content of ZnO is more than
24.1 vol%, the elongation at break decreased greatly, and
Qh hardness increased, which is deadly for elastomers and will
K⫽ (1)
A共T hot㛭int ⫺ Tcold㛭int兲 lead to the lose of its useful value.

126 POLYMER COMPOSITES—2007 DOI 10.1002/pc


TABLE 3. Average deviation between calculated and experimental
thermal conductivities for each volume fraction.

Average deviation (%)

Volume fraction (vol%) Nielsen Agari

4.3 4.37 3.11


12.0 4.00 0.95
18.5 2.79 3.68
21.4 4.15 4.56
24.1 8.54 3.90
31.2 28.17 0.81
34.6 47.36 5.98

Effective thermal conductivities of the composite were cal-


culated from the above equations, and experimental data were
FIG. 1. Comparison of thermal conductivity of ZnO filled silicone rubber compared with values predicted by the two equations (Fig. 1).
with theoretical predictions.
From Fig. 1, it can be observed that the predictions of Nielsen
model deviated significantly from the experimental data in the
range above 25 vol% of ZnO, and this model overestimates at
Thermal conductivities of silicone rubber filled with var- higher filler loading. The reason for the deviations is probably
ious contents of ZnO (1#) are indicated in Fig. 1. In the that the theoretical models did not take into account the state of
dispersion system with low volume content of ZnO, few filler dispersion in the composite. Another factor is probably
particles contribute to form conductive chains, and at this that each model shows good agreement with experimental
time the matrix polymer is almost continuous. Thus, the data, only in certain composite systems [34]. Of the expres-
contribution of fillers to the thermal conductivity of a com- sions tested, the experimental data are well-fitted into the Agari
posite seems to be less than that of the matrix, so that the model. A possible explanation is that the ease for the formation of
composites show low thermal conductivities. With the in- conductive chains was taken into account in the Agari model.
creasing of ZnO content, many ZnO particles touch each The average deviations between predicted and experi-
other to begin to form ZnO conductive chains, which greatly mental conductivities are shown in Table 3 as a function of
contribute to the thermal conductivities of composites. volume fraction of filler. Each data in Table 3 represents an
Typical theoretical models that were used to predict the average for the seven silicone composite systems. The Agari
thermal conductivities with high volume contents of parti- equation gives better agreement with the data up to 30 vol%,
cles are Agari and Nielsen Lewis models. and the Nielsen equation is also more accurate in the range
Nielsen equation: of 0 –20 vol%. On an overall basis, the average deviation
between calculated and measured conductivities is 3.28%
K c 1 ⫹ ABVf Kf/Kp ⫺ 1 1 ⫺ Vm for the Agari equation and 14.20% for the Nielsen equation
⫽ B⫽ ␾⫽1⫹ (2)
Kp 1 ⫺ BVf␾ Kf/Kp ⫹ A V2m By fitting our experimental data into the Agari model, a
possible explanation of the state of filler dispersion in our
thermal pads could be obtained. After a series calculation
Agari equation:
according to Eq. 3, C1 and C2 can be obtained. It can be
observed that the addition of ZnO fillers into the silicone
log Kc ⫽ VfC2 logKf ⫹ Vp log共C1 Kp兲 (3) rubber matrix will affect the C2 value (0.3248) more strongly
than the C1 value (0.9987). It has been reported that in the
In the two equations, Kc is the thermal conductivity of the preparation of a composite, particles can affect crystallinity and
composite, Kf is the thermal conductivity of the filler, Kp is crystal size of the polymer and change the thermal conductivity
the thermal conductivity of the polymer, A is a constant of the polymer [28], which is also the reason that C1 was
related to the generalized Einstein coefficient kE, B is a introduced. According to our results, C1 value is very closer to
constant related to the relative conductivity of the compo- 1, which indicates that ZnO fillers have little effect on the
nents, Vm is a function related to the maximum packing secondary structure of the silicone rubber. C2 is a factor of ease
volume fraction, ⌽ is a function related to Vm, Vf, and Vp the in forming conductive chains of particles, and the more easily
volume fraction of fillers and polymer respectively. C1 is particles are gathered to form conductive chains, the more
related with the crystallinity of the matrix, and C2 presents thermal conductivity of particles contributes to change that of
the ease for the formation of conductive chains [28]. Ac- composite. The obtained C2 value proved that it was not very
cording to Agari, the values of C1 and C2 should be between easy to form thermally conductive chains in the systems of
0 and 1. The closer C2 values are to 1, the more easily silicone rubber filled with ZnO, which is just not taken into
conductive chains are formed in the composite. account in Nielsen model.

DOI 10.1002/pc POLYMER COMPOSITES—2007 127


FIG. 3. Thermal conductivity of silicone rubber filled with hybrid ZnO
FIG. 2. Thermal conductivity of silicone rubber filled with fixed volume
particles.
content of hybrid ZnO particles.

Thermal Conductivity of Silicone Rubber Filled With according to the particle size distribution [12]. In highly
Hybrid ZnO Particles filled polymers, the effect of the particle size distribution on
Electric conduction system of composites changes from the polymer’s bulk property can be explained by the maxi-
dispersed system to attached system when volume content mum packing fraction (⌽m; ⌽m ⫽ real volume of the
of conductive particles increases [35]. Since the thermal filler/apparent volume of the filler), which means ⌽m will
conduction system has some analogy with the electric con- change as the particle size distribution of the filler changes.
duction system, thermal conductivity of the attached system The general approach for obtaining a high packing fraction
is much higher than that of the dispersed system. From the is to use small size particles to fill in the pores in the packed
above analysis, it can be found that the formation of the structure obtained from large-size particles. When the two
thermal conductive chains is mainly connected with the kinds (even more kinds) of differently sized fillers are
volume content of conductive fillers. The more the conduc- packed closely enough, ⌽m can reach a maximum, and
tive particles, the more conductive chains can be formed. some of the bulk properties of the polymer will also reach
But if we can obtain more thermal conductive chains with some extreme value. The sketch maps (Fig. 4) give a very
the same particles content, i.e., get higher thermal conduc- clear explanation. Figure 4a– 4c show thermal conduction
tivity with lower volume content of filler, the contradiction models filled by single, two hybrid, and three hybrid parti-
between high thermal conductivity and good processing cles, respectively. And we can find from the sketch maps
behavior can be solved in certain degree. that ⌽m of the three hybrid particles is the greatest and ⌽ m
Figure 2 is thermal conductivities of two hybrid particles of the single hybrid particles is the least. As shown in Figs.
(1# and 3# ZnO) filled silicone rubber with fixed filler 2 and 3, the thermal conductivity, as one of the silicone
volume content. As shown in Fig. 2, all of the samples had rubber’s bulk properties, changed as the particle size distri-
the same total quantity of filler (the total volume fraction of bution did. So, we conclude that it is the optimum particle
the filler was 0.314), and the particle size of the fillers (0.15 sizes and quantities that made the filler packing closer,
and 76 ␮m) did not change. The data in Fig. 2 showed that which thus led to formation of more thermal conductive
thermal conductivity reached a maximum as the hybrid ratio chains.
changed, which indicates silicone rubber incorporated by
hybrid particles can exhibit higher thermal conductivity,
Morphology Observation
compared with the case of only a single particle size.
Figure 3 is thermal conductivities of composites with The state of filler distribution is important, as under the
each size particle. It can be found that the size of particles percolation theory, filler units need to touch one another to
had little effect on thermal conductivity, while with the form a continuous heat conduction path [11]. Figure 5 is the
addition of the small-size particles (2# and 3# ZnO) into the SEM micrographs of the 1# ZnO (Fig. 5a and 5b) and (1# ⫹ 3#)
silicone rubber filled with 1# ZnO particles, the thermal ZnO (Fig. 5c and 5d) filled silicone rubber. Both the samples
conductivity of silicone rubber can be improved, i.e., we can are at 31.4 vol% filler loading. From Fig. 5b and 5d, it can be
get equal thermal conductivity with lower content of hybrid found that the particles were with light margin, and conductive
fillers, while with higher content of a single size of fillers. chains are observed in both the samples, indicating that per-
For a polymer filled with particles, many bulk properties, colation threshold has been reached at 31.4 vol% filler loading.
such as the modulus and dielectric constant, also change And there appeared some domains that are similar to the case

128 POLYMER COMPOSITES—2007 DOI 10.1002/pc


FIG. 4. Sketch maps of thermal conduction models (a) single filled particles; (b) two hybrid filled particles; (c)
three hybrid filled particles. Size: particle-1 ⬎ particle-2 ⬎ particle-3.

listed in Fig. 4. However, comparison between the broken Variation of Thermal Conductivity of Composite With
surfaces of the two samples (Fig. 5a and 5c) showed that the Temperature
(1# ⫹ 3#) ZnO fillers are more densely packed than 1# ZnO
fillers in the silicone rubber matrix, which is also an important Figure 6 shows the thermal conductivities of silicone
proof for the higher thermal conductivity in (1# ⫹ 3#) ZnO filler with ZnO at various temperatures. At low content of
filled silicone rubber. particles (dispersed system), the thermal conductivities of

FIG. 5. Tensile broken surfaces of 31.4% 1#ZnO filled silicone rubber. (a) ⫻10,000; (b) ⫻5,000; (1# ⫹ 3#)
ZnO filled silicone rubber (c) ⫻10,000; (d) ⫻5,000.

DOI 10.1002/pc POLYMER COMPOSITES—2007 129


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130 POLYMER COMPOSITES—2007 DOI 10.1002/pc